JP6378902B2 - Hydrotreating catalyst, method for producing the catalyst, and hydrotreating method for hydrocarbon oil using the catalyst - Google Patents

Description

  The present invention relates to a hydrotreating catalyst for removing impurities such as sulfur and nitrogen contained in hydrocarbon oil, a method for producing the catalyst, and a method for using the catalyst.

In recent years, there has been a strong demand for further improvement in the performance of hydrotreating catalysts that perform hydrorefining of distillate oil, which is the main fuel, in light of the global trend for improving the atmospheric environment.
In general, a hydrocarbon oil hydrotreating catalyst is generally prepared by firing and supporting a hydrogenation active metal component such as molybdenum and cobalt or nickel on an inorganic heat-resistant carrier such as alumina or silica.
However, in recent years, in order to further improve the catalyst performance, various ideas and proposals have been made for the reforming of the carrier and the method for supporting the catalytic metal as exemplified below.

Patent Document 1 discloses an active ingredient selected from Group 6B and Group 8 elements on an alkaline earth metal oxide-silica-alumina carrier containing 0.1 to 10% by weight of an alkaline earth metal oxide. A hydrotreating catalyst is proposed.
However, since the specific surface area of the catalyst is as high as 200 m ² / g or more, the average pore diameter is narrow, and the diffusion of hydrocarbon molecules in the catalyst pores is insufficient. There remains a problem that it cannot sufficiently cope with desulfurization of the oil.

Patent Document 2 proposes a catalyst in which a Group VIB metal, a Group VIII metal, phosphorus and an organic additive are present in a conventional oxide support as a catalyst for performing ultra-deep desulfurization of hydrocarbon oil.
However, Patent Document 2 lacks specific information related to optimization of carrier reforming and physical properties of the catalyst, and it is difficult to develop a catalyst with optimized desulfurization and denitrogenation activity based on the description of this document. It is.

Patent Document 3 proposes a hydrodesulfurization and denitrification catalyst in which a Group VIa metal, a Group VIII metal and a dihydric alcohol are supported on an oxide support containing silica, magnesia, and alumina.
However, the amount of magnesia contained in the catalyst is very large as 12 to 35% by weight (calculated value) on the basis of the carrier, and it has a drawback that it is difficult to control the pore properties and acidity of the carrier based on silica or alumina.

Patent Document 4 proposes a carbonaceous feedstock hydrotreating catalyst comprising an amorphous silica-alumina catalyst support containing at least one metal and a modifier.
Examples of the catalyst support applicable here include silica-alumina-zirconia, silica-alumina-thorium oxide, silica-alumina-titanium oxide, and silica-alumina-magnesium oxide. No specific manufacturing method or composition is disclosed. Therefore, it is difficult to develop a catalyst with optimized desulfurization and denitrogenation activity based on the description in this document.

JP 2000-5601 A JP 2000-313890 A JP 2001-310133 A Special table 2012-532212 gazette

  The problem to be solved by the present invention is as a hydrotreating catalyst for hydrocarbon oils, a catalyst having a hydrotreating (hydrogenation, desulfurization, denitrogenation) performance superior to conventional ones, a production method thereof, and the catalyst It is in the provision of the hydrotreating method of hydrocarbon oil using.

  In view of the above-mentioned problems of the prior art, the present inventors have conducted extensive research focusing on efficient reforming of the pore surface of the catalyst support and optimization of the pore structure. It was found that a catalyst obtained by supporting a hydrogenation active component and an organic additive on a silica-alumina support containing a metal of Group 2 of the periodic table is extremely effective for hydrotreating hydrocarbon oils. It came to complete.

  That is, the present invention provides an inorganic porous support containing at least one metal selected from Group 2 metals of the periodic table in addition to alumina and silica, to at least one metal selected from Group 6 metals of the periodic table, It is a hydrotreating catalyst of hydrocarbon oil carrying at least one metal selected from Table 8-10 metals and organic additives.

In the hydrotreating catalyst of the present invention, the content of at least one metal selected from Group 2 metals of the periodic table is 0.3 to 2% by mass based on the oxide catalyst, and the content of silica is an oxide. 5 to 10% by mass based on the catalyst. The average pore diameter is 10 to 20 nm, the specific surface area is 100 to 160 m ² / g, and the total pore volume is 0.3 to 0.6 ml / g.

  The method for producing a hydrocarbon oil hydrotreating catalyst according to the present invention includes calcining a hydrate containing at least one metal selected from Group 2 metals of the periodic table in addition to alumina and silica at 730 to 860 ° C. An impregnating solution containing at least one metal selected from Group 6 metals of the periodic table, at least one metal selected from Group 8 to 10 metals of the periodic table, and an organic additive in the inorganic porous carrier obtained as described above And the organic additive is dried under the condition that the organic additive remains on the catalyst so that the mass reduction ratio becomes 3 to 60% by mass.

Furthermore, the hydrotreating method of the hydrocarbon oil of the present invention comprises a hydrocarbon oil and a hydrotreating catalyst of the present invention, wherein the reaction temperature is 300 to 450 ° C., the hydrogen partial pressure is 1 to 20 MPa, the liquid space velocity is 0.1 to 10 hr ^{−. 1} , contact with hydrogen / oil ratio of 50 to 1,200 Nm ³ / kl.

  By using the hydrotreating catalyst of the present invention, impurities such as sulfur and nitrogen are efficiently removed from the hydrocarbon oil more than the conventional catalyst, and the hydrocarbon oil can be upgraded.

(1) Carrier Hereinafter, the present invention will be described in detail. The carrier used for the catalyst of the present invention contains a specific amount of a Group 2 metal oxide in the periodic table with silica-alumina as a base.
As the silica raw material, various silicon compounds such as alkali metal silicate, alkoxysilane, silicon tetrachloride, orthosilicate ester, silicone, silica sol, silica gel and the like can be used.
In addition, alumina raw materials include aluminum hydroxide (bayerite, gibbsite, diaspore, boehmite, pseudoboehmite, etc.), chloride, nitrate, sulfate, alkoxide, alkali metal aluminate, other inorganic salts, organic salts, Alumina sol can be used.
On the other hand, as raw materials for Group 2 metal oxides of the periodic table, oxides, halides (fluorides, chlorides, bromides, iodides, the same shall apply hereinafter), hydroxides, hydrides, nitrates, carbonates, sulfuric acids Examples include salts and organic acid salts. As the Group 2 element of the periodic table, magnesium, calcium, strontium, and barium can be applied, but magnesium and calcium are preferable, and magnesium is particularly preferable from the viewpoint of activity.

The silica-alumina-periodic table Group 2 metal oxide support can be obtained by firing silica-alumina hydrate containing a Group 2 metal prepared by a coprecipitation method or a kneading method.
The hydrate includes silica, coprecipitation of an alumina raw material and a Group 2 metal compound, alumina hydrate, kneading of a silicon compound and a Group 2 metal compound, and an alumina-Group 2 metal hydrate. It can be prepared by various methods such as mixing with a silicon compound or kneading a mixture of a silicon compound-Group 2 metal and alumina hydrate.
Silica-alumina-silica component after supporting the hydrogenation active metal or organic additive on the Group 2 metal oxide support of the periodic table and catalyzing is 3 to 12% by mass, preferably 5 to 5% based on the oxide catalyst. It is 10 mass%, More preferably, it is 6-9 mass%.
On the other hand, the Group 2 metal oxide of the periodic table is 0.3 to 2% by mass, preferably 0.4 to 1.8% by mass, more preferably 0.5 to 1.5% by mass based on the oxide catalyst. is there.

Silica-alumina hydrate containing a Group 2 metal in the periodic table contains hydrochloric acid, sulfuric acid, nitric acid, organic acids (formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, Malic acid, tartaric acid, citric acid, gluconic acid, etc.), aqueous solution of ammonia, sodium hydroxide, etc. is added to perform the peptization operation, and after kneading to improve moldability, the desired shape (pellet, sphere, extrusion) Etc.).
The molded article is usually 730 to 860 ° C. in the air (as the material temperature of the molded article, not the ambient temperature), preferably 740 to 850 ° C., more preferably 750 to 840 ° C. for 0.1 to 3 hours. The calcined carrier is preferably 0.5 to 2 hours.

The hydrogenation active component and the organic additive are added to the support obtained in the above step, and these are supported by drying treatment.
The addition method is not particularly limited, and various industrial methods such as impregnation method, coating method, spraying method and the like can be applied, but the impregnation method is preferable from the viewpoint of workability and addition efficiency. The impregnation method, adsorption method, equilibrium adsorption method, pore filling method, incipient wetness method, evaporation to dryness method, spray method, etc. are all applicable to the present invention, but from the viewpoint of workability, the pore filling method Is preferred.
The order of addition of the hydrogen active component and the organic additive is not particularly limited, and can be added sequentially or simultaneously. In the case of the impregnation method, a solution in which each component is dissolved in various polar organic solvents, water, or a water-polar organic solvent mixture can be used, but the most preferable solvent is water.

(2) Supported component The Group 6 element of the periodic table among the supported hydrogenation active components is at least one selected from chromium, molybdenum, and tungsten. These elements can be used alone, and in that case, molybdenum, tungsten, and particularly molybdenum are preferable from the viewpoint of economy and activity.
Moreover, you may use it combining according to the reactivity of raw material oil, or the operating conditions of a reactor. In the case of combination, chromium-molybdenum, chromium-tungsten, molybdenum-tungsten, chromium-molybdenum-tungsten can be exemplified.
The supported amount is 10 to 40% by mass, preferably 15 to 35% by mass, and more preferably 20 to 30% by mass as a total of all Group 6 element oxides of the periodic table. If it is less than 10% by mass, the catalyst activity is low, and if it exceeds 40% by mass, there is no increase in activity.
Examples of the raw material of the Group 6 element of the periodic table include chromate, molybdate, tungstate, trioxide, halide, heteropolyacid, heteropolyacid salt and the like.

Examples of the Group 8-10 elements of the periodic table of the hydrogenation active component include iron, cobalt, and nickel. Each of these elements can be used alone, and cobalt and nickel are preferred from the viewpoints of economy and activity.
Furthermore, it can also be used in combination according to the reactivity of the feedstock and the operating conditions of the reactor. In the case of a combination, iron-cobalt, iron-nickel, cobalt-nickel, iron-cobalt-nickel can be exemplified.
The supported amount is 0.5 to 15% by mass, preferably 1 to 10% by mass, and more preferably 2 to 6% by mass on the basis of the oxide catalyst as the sum of all group 8-10 element oxides of the periodic table. If the supported amount is less than 0.5% by mass, the catalytic activity is insufficient, and if it exceeds 15% by mass, there is no increase in activity.
As the iron, cobalt and nickel compounds used for loading, oxides, hydroxides, halides, sulfates, nitrates, carbonates, organic acid salts and the like can be used.
When preparing the impregnation solution of the hydrogenation active component, each of the periodic table group 6 elements and the periodic table groups 8 to 10 elements may be prepared independently, or a homogeneous solution in which both are mixed may be used.

In order to improve the pH adjustment of the solution, the liquid stability and the hydrogenation activity of the catalyst, the impregnation solution of the hydrogenation active component is aqueous ammonia, hydrogen peroxide, nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, Hydrofluoric acid or the like may be added.
In addition, phosphoric acid can also be added as a catalyst component, and the addition amount range in that case is 0.5 to 15% by mass, preferably 1 to 10% by mass, more preferably 1 to 10% by mass as phosphorous oxide based on the oxide catalyst It is 2-8 mass%. Examples of phosphoric acid that can be added include orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphonic acid, diphosphonic acid, phosphinic acid, polyphosphoric acid, their organic salts, and inorganic salts.
In addition to adding the phosphoric acid to the impregnation liquid of the hydrogenation active component, a part or all of the addition amount may be contained in the preparation process of the silica-alumina-periodic table group 2 metal oxide support.

  Organic additives are water-soluble organic compounds as shown below, such as polyhydric alcohols and their ethers, polyhydric alcohols or ether esters, saccharides, carboxylic acids and their salts, amino acids and their Selected from salts, various chelating agents and the like.

  Examples of polyhydric alcohols and ethers thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, isopropylene glycol, dipropylene glycol, tripropylene glycol, butanediol (1,2-, 1,3-, 1 , 4-, 2,3-), pentanediol (for example, 1,5-, including other isomers), 3-methyl-1,5-pentanediol, neopentyl glycol, hexanediol (for example, 1,2- 1,6-, including other isomers), hexylene glycol, polyvinyl alcohol, polyethylene glycol (average molecular weight 200 to 600), polypropylene glycol (limited to water solubility), glycerin, trimethylolethane, trimethylolpropane, Hexanetriol (eg, 1.2) , 6-, including other isomers), polyhydric alcohols such as erythritol and pentaerythritol, and ethers thereof (methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl and any of these) And water-soluble monoethers, diethers, and triethers selected from the above combinations).

  Examples of the esters of polyhydric alcohols or ethers include the above-mentioned polyhydric alcohols or esters of the ethers (monoesters such as formic acid and acetic acid, diesters and triesters which are water-soluble).

  Examples of the saccharide include saccharides such as glucose, fructose, isomerized sugar, galactose, maltose, lactose, sucrose, trehalose, starch, dextrin, pectin, glycogen, and curdlan.

  Carboxylic acids and their salts include formic acid, acetic acid, propionic acid, succinic acid, malonic acid, succinic acid, maleic acid, fumaric acid, tartaric acid, citric acid (anhydride, monohydrate), malic acid, gluconic acid, Examples thereof include carboxylic acids such as glutaric acid and salts thereof.

  Examples of amino acids and salts thereof include amino acids such as aspartic acid, alanine, arginine, glycine, and glutamic acid, and salts thereof.

Various chelating agents include ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid. (HEDTA), diethylenetriaminepentaacetic acid (DTPA), triethyltetraamminehexaacetic acid (TTHA), hydroxyethyliminodiacetic acid (HIDA), 1,3-propanediaminetetraacetic acid (PDTA), 1,3-diamino-2-hydroxypropane Tetraacetic acid (PDTA-OH), trans-1,2-cyclohexanediaminetetraacetic acid (CyDTA), glycol ether diaminotetraacetic acid (GEDTA), nitrilotriacetic acid (NTA), dihydroxy Glycine (DHEG), (S, S) - ethylenediamine -N, various chelating agents such as N'- disuccinic acid (EDDS) are exemplified.
The above organic additives can be used alone or in appropriate combination.

The addition amount of the organic additive is 0.05 to 3 times the total number of moles of the periodic table group 6 element and the periodic table group 8 to 10 elements, preferably 0.08 to 2.8 times, Particularly preferably, the amount is 0.1 to 2.5 times. If the amount is less than 0.05 moles, no improvement in catalyst performance is observed. There is no increase in activity beyond the 3-fold mole.
Although there is a relationship with the addition of the hydrogenation active component, the order of addition of the hydrogenation active component and the organic additive is not limited. That is, it may be added as a separate solution before or after the addition of the hydrogenation active component, or may be added simultaneously as a homogeneous solution with the hydrogenation active component. Further, the hydrogenation active component solution, the organic additive solution or a homogeneous solution thereof may be added at once or divided into a plurality of times depending on the viscosity of the solution and the pore volume (water absorption amount) of the carrier.

After completing the addition of the hydrogenation active component and the organic additive, the drying process described later is performed to complete the periodic table group 6 element, the periodic table group 8 to 10 element, and the organic additive supported on the carrier. It becomes a catalyst. When the above components are supported, a catalyst having an activity superior to that of the conventional calcined catalyst can be obtained by stopping by the drying treatment and not firing.
In this drying process, organic additives do not change the basic skeletal structure (addition and desorption of water of crystallization, hydrogen ions, hydroxide ions, ammonium ions, etc. are not taken into account), at least a part of which is hydrogenating activity It is desirable that the components remain by interacting with each other (intermolecular force, hydrogen bond, covalent bond, ionic bond, coordination bond, etc.).
As a measure of the remaining ratio of the organic additive, the mass reduction ratio when the finished catalyst is heated in air at 550 ° C. for 1 hour is 3 to 60 mass%, preferably 4 to 55 mass%, particularly preferably 5 to 50 mass%. It is preferable to be within the range. When the mass reduction ratio is less than 3% by mass, volatilization and decomposition of the supported organic additive occurs, and the catalytic activity is improved due to insufficient interaction with the hydrogenation active metal component. Absent. In the case of exceeding 60% by mass, the organic additive flows out with a large amount of water produced during the preliminary sulfidation step, and the catalytic activity cannot be improved.

The drying method is not particularly limited as long as the interaction between the organic additive and the hydrogenation active component as described above can be maintained. For example, convection heat transfer drying (hot air drying), radiant heat transfer drying (infrared, far infrared drying), conduction heat transfer drying, microwave drying, freeze drying, vacuum drying, etc. Industrial techniques can be applied. The drying conditions are not particularly limited, and can be appropriately set according to the volatilization and decomposition conditions of the organic additive.
The simplest drying method is hot air drying. In this case, for example, in the air or in an inert gas (nitrogen gas, rare gas, carbon dioxide gas, low oxygen atmosphere, etc.), the basic skeleton of the organic additive as described above. As a temperature and time that do not change the temperature, for example, 30 to 250 ° C. (not as an ambient temperature but a dry substance temperature), preferably 50 to 220 ° C., more preferably 80 to 180 ° C., and still more preferably 90 to 150 Examples of the conditions include 0.1 to 3 hours at ° C. The substance temperature in the production stage of the catalyst of the present application is measured by any method used by those skilled in the art, for example, a thermocouple.

(3) Properties of the completed catalyst In order for the completed catalyst to exhibit good catalytic performance, it is desirable to have the following physical properties and pore structure. That is, the average pore diameter is 9 to 20 nm, preferably 10 to 18 nm, more preferably 11 to 16 nm. When the average pore diameter is less than 9 nm, the diffusion of the hydrocarbon oil in the pores is insufficient, and when it exceeds 20 nm, the specific surface area is decreased and the catalyst performance is decreased.
Further, the total pore volume is preferably 0.3 to 0.6 ml / g, more preferably 0.4 to 0.5 ml / g. If it is 0.3 ml / g or less, it is insufficient for diffusing the hydrocarbon oil into the pores. If it exceeds 0.6 ml / g, the absolute mass of the catalyst becomes light when the reactor is filled with the catalyst. (The amount of catalytically active component is reduced), so sufficient catalytic performance does not appear.
Here, as an index indicating the uniformity of the pores of the catalyst, the ratio of the pore volume having a diameter in the range of the average pore diameter ± 1.5 nm is 20 to 60% with respect to the total pore volume, preferably It is desirable to have a pore structure that is 22-58%. If it is less than 20%, the proportion of micropores that do not contribute to the reaction or large pores with a low surface area increases, and if it exceeds 60%, diffusion of the hydrocarbon oil having a relatively large molecular size into the pores is inhibited. This leads to a decrease in catalytic activity. The pore size distribution of the catalyst of the present invention is a unimodal distribution centering on the average pore diameter and its vicinity.
Specific surface area, 100~170m ² / g is desirable, more preferably in the range of 110~160m ² / g, more preferably from 115~150m ² / g. If it is less than 100 m ² / g, the catalyst performance is insufficient, and if it exceeds 170 m ² / g, the average pore diameter becomes too small, and pore clogging or the like tends to occur during the reaction.

  The pore structure (pore volume, average pore diameter, pore size distribution, etc.) is a value obtained by the mercury intrusion method (contact angle 140 °, surface tension 480 dyn / cm), and the specific surface area is a value obtained by the BET method. . When measuring the pore structure and specific surface area of the finished catalyst and determining the supported amount of the hydrogenation active component, the finished catalyst was treated at 450 ° C. in air for 1 hour to remove moisture and organic matter. The obtained analysis and measurement values are values based on oxide catalyst standards. Note that an X-ray fluorescence analyzer was used for quantification of the hydrogenation active component and the carrier component.

The catalyst is usually used after being subjected to a preliminary sulfidation operation, but this preliminary sulfidation operation can be performed inside or outside the reaction column.
As a preliminary sulfidation method, kerosene and light oil fractions containing sulfur in a heated state and hydrogen atmosphere are used, and carbon disulfide, butanethiol, dimethyl disulfide (DMDS), ditertiary nonyl polysulfide (TNPS) are used for these oils. It is possible to apply sulfidization in a liquid phase using a suitable amount of a sulfurizing agent such as a gas phase, or a gas phase sulfiding method using hydrogen sulfide or carbon disulfide as a sulfiding agent in a heated hydrogen stream.

(4) Hydrocarbon oil The hydrocarbon oil to be hydrotreated with the catalyst of the present invention has a 90% boiling point temperature of 560 ° C. or less, preferably 540 ° C., based on the ASTM D-2887 or D-2887 extended method. Hereinafter, it is a distillate having an initial boiling point of 100 ° C or higher, preferably 150 ° C or higher.
Specific examples include petroleum-based naphtha, straight-run kerosene, straight-run light oil, heavy light oil, vacuum gas oil, heavy vacuum gas oil, etc., from hydrocracking equipment, thermal cracking equipment and fluid catalytic cracking equipment. In addition to the kerosene fraction obtained (light cycle oil, coker diesel oil, etc.), kerosene fraction derived from heavy oil direct desulfurization equipment, fractions equivalent to kerosene derived from coal or animal and plant biomass, the distillates listed above Any mixed oil is also included.
The metal content such as vanadium and nickel in the raw material oil to be treated is 5 mass ppm or less, preferably 1 mass ppm or less, and the residual carbon content is 1 mass% or less, preferably 0.9 mass% or less. However, in order to satisfy the above-mentioned metal content and residual carbon content, the raw material distillate should be vacuum gas oil, atmospheric residue, vacuum residue, solvent defoaming oil, coal liquefied oil, shale oil, tar sand oil. It is also possible to mix and process heavy oil such as.

(5) Hydrotreating method The hydrotreating catalyst of the present invention is a reactor such as a fixed bed, a boiling bed, a moving bed, etc., in which the hydrocarbon oil is hydrogenated, hydrodesulfurized, hydrogenated in the presence of hydrogen. It can be used in various hydrotreating reactions for hydrodenitrogenation, hydrodeoxygenation, hydrocracking, hydroisomerization and the like. The hydrotreating catalyst of the present invention is more preferably used for desulfurization and denitrogenation of petroleum distillate, particularly reducing sulfur content in kerosene or light oil fraction to 80 mass ppm or less, and further to 10 mass ppm or less. That is.
When used in a hydrotreating apparatus, the reaction conditions depend on the type of raw material oil, but the hydrogen partial pressure is 1 to 20 MPa, preferably 3 to 18 MPa, the hydrogen / oil ratio is 50 to 1,200 Nm ³ / kl, preferably 100 ˜1,000 Nm ³ / kl, liquid space velocity 0.1 to 10 h ⁻¹ , preferably 0.5 to 8 h ⁻¹ , reaction temperature 300 to 450 ° C., preferably 320 to 430 ° C. It is.

The following examples further illustrate the present invention. However, the following examples do not limit the present invention.
(Preparation of catalyst)
Example 1
A silica-alumina hydrate gel (silica / alumina mass ratio: 8.5 / 91.5) is prepared by adding and mixing aluminum sulfate, sodium aluminate and water glass into a tank containing hot tap water. did.
After separating the hydrate from the solution and washing away impurities using warm water, nitric acid was added, then magnesium carbonate (based on oxide catalyst, 0.5% by mass as magnesium oxide) was added, and the kneader was After adjusting the moisture content by heating and kneading, extrusion molding was carried out, followed by calcination in air at 780 ° C. for 1.5 hours to obtain a silica-alumina-magnesia carrier.
Molybdenum trioxide, basic cobalt carbonate, phosphoric acid, and organic additives so that the carrier is 22% by mass of molybdenum trioxide, 4% by mass of cobalt oxide, and 3% by mass of phosphorus oxide based on the oxide catalyst. Citric acid monohydrate, polyethylene glycol (average molecular weight 200) (The organic additive is 0.1 times the moles of citric acid monohydrate and polyethylene glycol, and 0.1 mol, respectively, relative to the total number of moles of molybdenum and cobalt. A catalyst A was obtained by impregnating an aqueous solution containing 3 times the molar amount) and drying with hot air in air for 2 hours under the condition that the temperature of the impregnated product was 120 ° C.
Table 1 shows the physical properties and chemical composition of Catalyst A.

(Example 2)
Example 1 Example 1 except that citric acid monohydrate and polyethylene glycol (average molecular weight 200), which are organic additives, were used in a molar amount 0.05 times the total number of moles of molybdenum and cobalt. Catalyst B was prepared in the same manner as above.
Table 1 shows the physical properties and chemical composition of Catalyst B.

(Example 3)
Catalyst C was prepared in the same manner as in Example 1, except that the amount of magnesium carbonate added was 0.8% by mass as magnesium oxide based on the oxide catalyst.
The physical properties and chemical composition of the catalyst C are shown in Table 1.

Example 4
Catalyst D was prepared in the same manner as in Example 1 except that calcium carbonate was used instead of magnesium carbonate.
Table 1 shows the physical properties and chemical composition of catalyst D.

(Example 5)
Silica sol and pseudo boehmite powder are put into a kneader (silica / alumina mass ratio: 8.5 / 91.5), magnesium carbonate (based on oxide catalyst, 0.5% by mass as magnesium oxide), ion-exchanged water, citric acid Was added, kneaded, heated and kneaded to adjust the moisture content, extruded, and calcined in air at 780 ° C. for 1.5 hours to obtain a silica-alumina-magnesia carrier.
Molybdenum trioxide, basic nickel carbonate, phosphoric acid and organic additives so that the carrier is 22% by mass of molybdenum trioxide, 4% by mass of nickel oxide, and 5% by mass of phosphorus oxide based on the oxide catalyst. Impregnated with an aqueous solution containing diethylene glycol (the organic additive is added in a molar amount of 0.4 times the total number of moles of molybdenum and nickel), and the temperature of the impregnated product is 120 ° C. for 2 hours in the air The catalyst E was obtained by drying with hot air.
Table 1 shows the physical properties and chemical composition of the catalyst E.

(Comparative Example 1)
Alumina hydrate was prepared by adding and mixing aluminum sulfate and sodium aluminate to a tank containing hot tap water. After separating the hydrate from the solution and washing and removing impurities using warm water, nitric acid is added, and after adjusting the moisture content by heating and kneading using a kneader, extrusion molding, in the air, An alumina support was obtained by calcination at 680 ° C. for 1.5 hours.
Molybdenum trioxide, basic cobalt carbonate, phosphoric acid, and organic additives so that the carrier is 22% by mass of molybdenum trioxide, 4% by mass of cobalt oxide, and 3% by mass of phosphorus oxide based on the oxide catalyst. Citric acid monohydrate, polyethylene glycol (average molecular weight 200) (The organic additive is 0.1 times the moles of citric acid monohydrate and polyethylene glycol, and 0.1 mol, respectively, relative to the total number of moles of molybdenum and cobalt. A catalyst F was obtained by impregnating an aqueous solution containing 3 times the molar amount) and drying with hot air in air for 2 hours under the condition that the temperature of the impregnated product was 120 ° C.
The physical properties and chemical composition of catalyst F are shown in Table 1.

(Comparative Example 2)
Catalyst G was prepared in the same manner as in Example 1 except that magnesium carbonate was not used in Example 1 and the silica-alumina hydrate molded product was calcined at 890 ° C.
Table 1 shows the physical properties and chemical composition of the catalyst G.

(Comparative Example 3)
Catalyst H was prepared in the same manner as in Example 1 except that the amount of magnesium carbonate added was 2.1% by mass in Example 1.
Table 1 shows the physical properties and chemical composition of the catalyst H.

(Comparative Example 4)
Pseudo boehmite powder, ion-exchanged water and nitric acid are put into a kneading machine, kneaded thoroughly, heated and kneaded to adjust the moisture content, extruded, and calcined in air at 680 ° C. for 1.5 hours. An alumina support was obtained.
Molybdenum trioxide, basic nickel carbonate, phosphoric acid and organic additives so that the carrier is 22% by mass of molybdenum trioxide, 4% by mass of nickel oxide, and 5% by mass of phosphorus oxide based on the oxide catalyst. Impregnated with an aqueous solution containing diethylene glycol (the organic additive is added in a molar amount of 0.4 times the total number of moles of molybdenum and nickel), and the temperature of the impregnated product is 120 ° C. for 2 hours in the air The catalyst I was obtained by drying with hot air.
The physical properties and chemical composition of Catalyst I are shown in Table 1.

[Hydrogenation activity test]
1. Gas oil hydrotreating test After the catalysts of Examples 1 to 4 and Comparative Examples 1 to 3 were charged into a fixed bed small flow reactor, sulfurized oil in which dimethyl disulfide was added to the light oil in Table 2 (2.5% as total sulfur content). After preliminary sulfidation by the equivalent of mass%, the hydrotreating test was conducted under the conditions shown in Table 3 by switching to the feedstock oil in Table 2.
The sulfur content of the product oil obtained in the test was measured by the fluorescent X-ray method, and the specific activity based on volume was determined based on the formulas (1) and (2).
The test results are shown in Table 6.

  In the above formula, LHSV is the liquid space velocity, k is the reaction rate constant, n is the reaction order, X is in the feedstock, and Y is the mass proportion of sulfur in the product oil.

2. Gas oil hydrotreating test under reduced pressure The catalyst of Example 5 and Comparative Example 4 was charged into a fixed bed small flow reactor, and sulfur oil obtained by adding dimethyl disulfide to the light oil in Table 2 (corresponding to 2.5% by mass as the total sulfur content) ) Was then switched to the feedstock oil shown in Table 4, and a hydrogenation test of vacuum gas oil was conducted under the conditions shown in Table 5.
The sulfur content of the product oil obtained in the test was measured by the fluorescent X-ray method and the nitrogen content was measured by the oxidative decomposition chemiluminescence method, and the specific activity based on the capacity was determined based on the formulas (3) to (5).
The evaluation results are shown in Table 7.

  In the above formula, LHSV is the liquid space velocity, k is the reaction rate constant, n is the reaction order, X is the sulfur or nitrogen content in the feed oil, and Y is the mass proportion of sulfur or nitrogen content in the product oil. Note that ln is a natural logarithm.

The energy consumption index in Table 6 is the ratio of the numerical values of Examples 1 to 4 and Comparative Examples 1 to 3 with respect to the numerical values in Comparative Example 1 by converting the amount of fuel and electricity used in the preparation process of the catalyst into the amount of heat. Is multiplied by 100.

  The energy consumption index in Table 7 is the amount of fuel and electricity used in the preparation process of the catalyst, converted into heat, and the ratio of the numerical values in Comparative Example 4 and Example 5 to the numerical values in Comparative Example 4 was multiplied by 100. Is.

From the hydrotreating test results of light oil and vacuum gas oil (Tables 6 and 7), the hydrotreating catalyst using the silica-alumina-periodic group 2 metal oxide carrier of the present invention uses a conventional alumina carrier. It can be seen that the hydrodesulfurization and hydrodenitrogenation activities are superior to those of the used catalysts.
In addition, although the catalyst of the comparative example 2 uses the silica-alumina support | carrier which does not contain a periodic table group 2 metal, the light oil desulfurization activity is substantially equivalent to an Example.
However, in order to obtain a catalyst having the same pore structure as that of the example catalyst, a high calcination temperature is required in the carrier production process, so that there is a disadvantage that the energy cost is high in commercial production. .
It can be seen that the catalyst of the present invention is a highly economical catalyst that has higher catalytic activity than conventional ones, and has reduced energy consumption in terms of production.

Claims (8)

In addition to alumina and silica, an inorganic porous carrier containing at least one metal selected from Group 2 metals of the periodic table is used, and at least one metal selected from Group 6 metals of the periodic table is used. A hydrotreating catalyst for hydrocarbon oil carrying at least one metal selected from group metals and an organic additive ,
The content of at least one metal selected from Group 2 metals of the periodic table is 0.3 to 2% by mass based on the oxide catalyst,
The Group 8-10 metal of the periodic table is selected from iron, cobalt, nickel,
The organic additive is selected from the group consisting of polyhydric alcohols and their ethers, polyhydric alcohols or esters of ethers, saccharides, carboxylic acids and their salts, amino acids and their salts, and chelating agents. At least one,
The content of silica is 3 to 12% by mass based on the oxide catalyst,
The average pore diameter is 9 to 20 nm, the specific surface area is 100 to 170 m ² / g, and the total pore volume is 0.3 to 0.6 ml / g.
Said hydrotreating catalyst . The hydrotreating catalyst according to claim 1 , wherein the content of the organic additive is 0.05 to 3 times the total number of moles of the Group 6 element of the periodic table and the Group 8 to 10 elements of the periodic table. The hydrogen according to claim 1 or 2 , wherein the Group 2 metal of the periodic table is magnesium or calcium, the Group 6 metal of the periodic table is molybdenum or tungsten, and the Group 8-10 metal of the periodic table is cobalt and / or nickel. Catalyst. The hydroprocessing catalyst according to any one of claims 1 to 3 , wherein phosphoric acid is further supported as a catalyst component in an amount of 0.5 to 15% by mass based on the oxide catalyst. It is a manufacturing method of the hydroprocessing catalyst of any one of Claims 1-4,
In addition to alumina and silica, an inorganic porous support obtained by calcining a hydrate containing at least one metal selected from Group 2 metals of the Periodic Table at 730 to 860 ° C. is used. Impregnating an impregnating liquid containing at least one metal selected from the group consisting of at least one metal selected from Group 8 to 10 metals of the periodic table and an organic additive, so that the mass reduction ratio is 3 to 60% by mass. A method for producing a hydrotreating catalyst for hydrocarbon oil, wherein the organic additive is dried under the condition that the catalyst remains on the catalyst. The hydrogenation treatment according to claim 5 , wherein the Group 2 metal of the periodic table is magnesium or calcium, the Group 6 metal of the periodic table is molybdenum or tungsten, and the Group 8-10 metal of the periodic table is cobalt and / or nickel. A method for producing a catalyst. A hydrocarbon oil and the hydrotreating catalyst according to any one of claims 1 to 4 are mixed with a reaction temperature of 300 to 450 ° C, a hydrogen partial pressure of 1 to 20 MPa, a liquid space velocity of 0.1 to 10 hr ^-1 , hydrogen / A method for hydrotreating a hydrocarbon oil to be brought into contact under an oil ratio of 50 to 1,200 Nm ³ / kl. The hydrotreating method according to claim 7 , wherein the hydrocarbon oil is a distillate selected from the group consisting of petroleum-based naphtha, straight-run kerosene, straight-run light oil, heavy light oil, vacuum gas oil, and heavy vacuum gas oil. .